A new discrimination scheme for oceanic ferromanganese deposits using high field strength and rare earth elements

Abstract Ferromanganese (Fe-Mn) deposits constitute a ubiquitous mineral type in oceanic settings, with metal (Cu, Ni, Zn, Co, Pt) and rare earth element (REE) enrichments of potential economic interest. Routine analysis of trace elements by ICP-MS has advanced our understanding of the impact of hydrogenetic, diagenetic and hydrothermal processes on the mobility and interaction of high field strength elements (HFSE: Zr and Ti) and REE and yttrium (REY) with Fe-Mn oxyhydroxides. Recent discoveries in the French exclusive economic zone (EEZ) of Wallis and Futuna (southwest Pacific Ocean) have brought new insight into the formation of low temperature (LT) hydrothermal Mn deposits and lead us to reconsider the classification and discrimination diagrams for Fe-Mn deposits and ore-forming processes. Using a suite of LT hydrothermal Fe-Mn crusts from Wallis and Futuna, we investigate how contrasting genetic processes influence the distribution of metals (Mn, Fe, Cu, Ni, and Co), HFSE and REY in hydrogenetic, diagenetic, hydrothermal and mixed-type deposits from different environments in the global ocean. The interaction of the different metal oxide-forming processes indicates that: (i) enrichment of Co, HFSE and REY is favored by hydrogenetic precipitation, (ii) diagenetic processes produce higher Mn, Cu, and Ni concentrations with oxic remobilization in the sedimentary column, while suboxic conditions promote greater Mn and Fe remobilization that competes with the incorporation of Cu and Ni ions in nodules. HFSE and REY derived from seawater are usually low in diagenetic precipitates, which discriminate between hydrogenetic and diagenetic inputs within nodules, (iii) hydrothermal Fe-Mn deposits show strong depletion in HFSE and REY due to rapid formation and high contents of either Fe or Mn oxides. We present a new discrimination scheme for the genetic types of Fe-Mn deposits using a 10 ∗ (Cu + Ni + Co) − 100 ∗ (Zr + Y + Ce) − (Fe + Mn) / 4 ternary diagram. The use of HFSE and REY in the classification allows for a more robust discrimination of: (i) each ore-forming process with well-delimited fields, without overlap of metal-rich hydrothermal samples and hydrogenetic samples, (ii) oxic and suboxic diagenesis within nodules, (iii) trends between hydrogenetic and diagenetic end-members forming a continuum, and (iv) mixed genetic types such as the presence of hydrothermal particles within hydrogenetic crust layers. Alternatives are also explored to adapt our discriminative diagram to elements measurable by on-board instruments to aid in exploration at sea.